CN114456426A - High-strength polytetrafluoroethylene composite board and preparation method thereof - Google Patents
High-strength polytetrafluoroethylene composite board and preparation method thereof Download PDFInfo
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- CN114456426A CN114456426A CN202111624649.7A CN202111624649A CN114456426A CN 114456426 A CN114456426 A CN 114456426A CN 202111624649 A CN202111624649 A CN 202111624649A CN 114456426 A CN114456426 A CN 114456426A
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- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 122
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 122
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 22
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000003490 calendering Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000002019 doping agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 24
- 238000005245 sintering Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000002457 bidirectional effect Effects 0.000 description 4
- 239000012982 microporous membrane Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZJBHFQKJEBGFNL-UHFFFAOYSA-N methylsilanetriol Chemical compound C[Si](O)(O)O ZJBHFQKJEBGFNL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- Chemical Kinetics & Catalysis (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of materials, and particularly relates to a high-strength polytetrafluoroethylene composite board and a preparation method thereof. The invention solves the problem of poor mechanical property of the existing polytetrafluoroethylene plate, and achieves the effect of improving the mechanical property by utilizing trichloromethyl silane to form a silica system and forming a permeable structure with expanded polytetrafluoroethylene.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a high-strength polytetrafluoroethylene composite board and a preparation method thereof.
Background
The polytetrafluoroethylene is commonly called 'plastic king', is a high molecular polymer prepared by polymerizing tetrafluoroethylene as a monomer, is white and waxy, is semitransparent, has excellent heat resistance and cold resistance, and can be used at the temperature of minus 180-260 ℃ for a long time. And the polytetrafluoroethylene has the characteristics of acid resistance, alkali resistance and various organic solvents resistance, is hardly dissolved in all solvents, has the characteristic of high temperature resistance, and has extremely low friction coefficient. Therefore, polytetrafluoroethylene becomes an ideal coating for easily cleaning the inner layer of the water pipe.
However, the polytetrafluoroethylene material has good chemical inertness, which hinders the combination with other materials, so that the existing polytetrafluoroethylene plate is mainly made of pure polytetrafluoroethylene material, and the strength of the single polytetrafluoroethylene plate is generally not high, which greatly limits the application in the fields of chemical engineering, machinery and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-strength polytetrafluoroethylene composite board, which solves the problem of poor mechanical property of the existing polytetrafluoroethylene board, and achieves the effect of improving the mechanical property by forming a silica system by trichloromethylsilane and forming a permeable structure by expanded polytetrafluoroethylene.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a high-strength polytetrafluoroethylene composite board takes a polytetrafluoroethylene board as a substrate and a modified polytetrafluoroethylene film as a coating, wherein the coating takes polytetrafluoroethylene as a raw material and takes a silica material as a doping material; in the material, the polytetrafluoroethylene plate still keeps good chemical inertia and also can keep good high-temperature resistance, the silica material can keep good chemical inertia and also has good hydrophobic property, the hydrolysis resistance of the polytetrafluoroethylene material can be improved, and meanwhile, the silica structure of the silica material shows good chemical inertia, high-temperature resistance and mechanical strength, so that the problem of poor mechanical property of the polytetrafluoroethylene is solved.
The modified polytetrafluoroethylene coating is formed by calendering nano polytetrafluoroethylene into expanded polytetrafluoroethylene and modified by trichloromethylsilane steam doping to obtain the silica modified polytetrafluoroethylene composite board.
The preparation method of the modified polytetrafluoroethylene coating comprises the following steps:
a1, adding nano polytetrafluoroethylene into ethanol, stirring to form a uniform solution, standing and evaporating to form slurry, wherein the concentration of the nano polytetrafluoroethylene in the ethanol is 100-2000 g/L, the stirring speed is 1000-2000 r/min, and the standing and evaporating temperature is 80-90 ℃;
a2, placing the slurry on a calender for standing for 1-2 h at a constant temperature, and calendering to form a base film, wherein the temperature of the constant temperature standing is 80-90 ℃, the temperature of the calendering is 80-100 ℃, and the thickness of the base film after the calendering is 200-500 mu m;
a3, stretching, sintering and curing the base membrane to obtain the expanded polytetrafluoroethylene membrane; the stretching sequentially comprises longitudinal stretching, bidirectional stretching and transverse stretching, wherein the longitudinal stretching multiple is 2-4 times, the temperature is 250-260 ℃, the bidirectional stretching multiple is 2-4 times, the temperature is 220-240 ℃, and the transverse stretching temperature is 160-180 ℃; the sintering is carried out after the transverse stretching is finished, the sintering temperature is 320 ℃, the sintering time is 30-60 s, and the polytetrafluoroethylene-based microporous membrane with the thickness of 10-50 mu m and the pore diameter of 0.2-1.4 mu m is obtained after the sintering;
a4, adding trichloromethylsilane into anhydrous ether, and stirring uniformly to form a dissolved solution; then placing the expanded polytetrafluoroethylene membrane in a dry reaction kettle, introducing a dissolving solution at a constant temperature, standing for 20-30 min, and cooling to obtain a coated expanded polytetrafluoroethylene membrane; the concentration of the trichloromethylsilane in the anhydrous ether is 300-600 g/L, the constant temperature is 70-80 ℃, the introducing speed is 20-50 mL/min, the standing temperature is 70-80 ℃, and the temperature after temperature reduction is 40-60 ℃; trichloromethylsilane and anhydrous ether in the step are directly heated and converted into mixed steam of trichloromethylsilane and ether, the trichloromethylsilane directly permeates into micropores of the expanded polytetrafluoroethylene membrane in the process of introducing the steam into the reaction kettle, and is directly converted into liquid drops in the process of cooling, namely, a trichloromethylsilane liquid membrane is formed on the specific surface of the polytetrafluoroethylene membrane, and the ether still keeps a steam state;
a5, placing the expanded polytetrafluoroethylene membrane in the a4 in a reaction kettle, standing for 20-40 min, heating for 20-50 min, and then performing radiation treatment for 2-6 min to obtain the modified polytetrafluoroethylene coating, wherein the atmosphere of the reaction kettle is an atmosphere containing water vapor, the atmosphere consists of nitrogen and water vapor, and the volume ratio of the nitrogen to the water vapor is 20: 1-2, standing at 50-60 ℃; the temperature of the heating treatment is 200-230 ℃, the step utilizes water vapor to form hydrolysis reaction with trichloromethylsilane in the standing process, trihydroxymethylsilane is formed on the surface, the trihydroxymethylsilane is promoted to form dehydration condensation polymerization reaction under the temperature condition at the time, a silica system structure is formed, in addition, in the silica system, even a polytetrafluoroethylene microporous structure, radiation treatment can utilize the reflection characteristic and the permeation characteristic of the silica structure to enable radiation to act on the specific surface of polytetrafluoroethylene, residual hydroxyl in the silica structure and radiated polytetrafluoroethylene molecules to form reaction, and the combination of the silica system and the polytetrafluoroethylene material is improved, so that the performance of the polytetrafluoroethylene material is improved.
The preparation method of the high-strength polytetrafluoroethylene composite board comprises the following steps:
step 1, sequentially carrying out sanding treatment on coarse sand and fine sand on the surface of a polytetrafluoroethylene plate to form a polytetrafluoroethylene plate with a concave-convex surface;
step 2, spraying a liquid film on the surface of the polytetrafluoroethylene plate with the concave-convex surface, then attaching the modified polytetrafluoroethylene coating to the surface of the polytetrafluoroethylene plate, and standing at constant temperature for 20-30 min to obtain a prefabricated composite plate; the spraying amount is 2-5 mL/min by adopting anhydrous ether; the temperature of the constant-temperature standing is 50-60 ℃;
and 3, performing constant-temperature extrusion treatment on the prefabricated composite board for 2-4 h, cooling to obtain the high-strength polytetrafluoroethylene composite board, wherein the constant-temperature extrusion temperature is 270-300 ℃, and the pressure is 0.4-0.7 Mpa, the surface of the polytetrafluoroethylene board with concave-convex surface is softened by using the temperature in the process, and the coating is permeated in the extrusion process, namely the concave-convex structure on the surface and the micropores of the expanded polytetrafluoroethylene coating are mutually permeated and staggered, and the polytetrafluoroethylene is used as a homogeneous material, so that good connectivity can be achieved, and the composite board is ensured to be integrated.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of poor mechanical property of the existing polytetrafluoroethylene plate, and the trichloromethylsilane is used for forming a silica system and the expanded polytetrafluoroethylene forms a permeable structure, thereby achieving the effect of improving the mechanical property.
2. The invention utilizes the modified polytetrafluoroethylene membrane as the surface coating of the polytetrafluoroethylene plate, fully utilizes the homogeneity characteristic of the polytetrafluoroethylene and achieves a compact integrated structure.
3. The surface of the polytetrafluoroethylene plate is frosted, so that the concave-convex structure of the surface is realized, and the microporous structure of the expanded polytetrafluoroethylene coating is matched to form the staggering of permeability, so that the aim of improving the strength of the coating and the polytetrafluoroethylene plate is fulfilled.
Detailed Description
A specific embodiment of the present invention will be described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
The high-strength polytetrafluoroethylene composite board takes a polytetrafluoroethylene board as a substrate and a modified polytetrafluoroethylene film as a coating, wherein the coating takes polytetrafluoroethylene as a raw material and takes a silica material as a doping material.
The coating of the modified polytetrafluoroethylene is prepared by calendering nano polytetrafluoroethylene to form expanded polytetrafluoroethylene and modifying the expanded polytetrafluoroethylene by trichloromethylsilane steam doping, and the preparation method of the coating comprises the following steps: a1, adding nano polytetrafluoroethylene into ethanol, stirring to form a uniform solution, standing and evaporating to form slurry, wherein the concentration of the nano polytetrafluoroethylene in the ethanol is 100g/L, the stirring speed is 1000r/min, and the standing and evaporating temperature is 80 ℃; a2, placing the slurry on a calender, standing for 1h at a constant temperature, calendering to form a base film, wherein the temperature of the constant temperature standing is 80 ℃, the temperature of the calendering is 80 ℃, and the thickness of the calendered base film is 200 mu m; a3, stretching, sintering and curing the base membrane to obtain the expanded polytetrafluoroethylene membrane; the stretching sequentially comprises longitudinal stretching, biaxial stretching and transverse stretching, wherein the longitudinal stretching multiple is 2 times, the temperature is 250 ℃, the biaxial stretching multiple is 2 times, the temperature is 220 ℃, and the transverse stretching temperature is 160 ℃; the sintering is carried out after the transverse stretching is finished, the sintering temperature is 300 ℃, the sintering time is 30s, and the polytetrafluoroethylene-based microporous membrane with the thickness of 10 mu m and the pore diameter of 0.2 mu m is obtained after the sintering; a4, adding trichloromethylsilane into anhydrous ether, and stirring uniformly to form a dissolved solution; then placing the expanded polytetrafluoroethylene membrane in a dry reaction kettle, introducing a dissolving solution at a constant temperature, standing for 20min, and cooling to obtain a coated expanded polytetrafluoroethylene membrane; the concentration of trichloromethylsilane in anhydrous ether is 300g/L, the constant temperature is 70 ℃, the introducing speed is 20mL/min, the standing temperature is 70 ℃, and the temperature after temperature reduction is 40 ℃; a5, placing the expanded polytetrafluoroethylene membrane in the a4 in a reaction kettle, standing for 20min, heating for 20min, and then radiating for 2min to obtain the modified polytetrafluoroethylene coating, wherein the atmosphere of the reaction kettle is an atmosphere containing water vapor, the atmosphere consists of nitrogen and water vapor, and the volume ratio of the nitrogen to the water vapor is 20: 1, standing at 50 ℃; the temperature of the temperature raising treatment is 200 ℃.
The preparation method of the high-strength polytetrafluoroethylene composite board comprises the following steps:
step 1, sequentially carrying out sanding treatment on coarse sand and fine sand on the surface of a polytetrafluoroethylene plate to form a polytetrafluoroethylene plate with a concave-convex surface;
step 2, spraying a liquid film on the surface of the polytetrafluoroethylene plate with the concave-convex surface, then attaching the modified polytetrafluoroethylene coating to the surface of the polytetrafluoroethylene plate, and standing at constant temperature for 20min to obtain a prefabricated composite plate; the spray adopts anhydrous ether, and the spray amount is 2 mL/min; the temperature of the constant-temperature standing is 50 ℃;
and 3, carrying out constant-temperature extrusion treatment on the prefabricated composite board for 2h, and cooling to obtain the high-strength polytetrafluoroethylene composite board, wherein the constant-temperature extrusion temperature is 270 ℃, and the pressure is 0.4 MPa.
Example 2
The high-strength polytetrafluoroethylene composite board takes a polytetrafluoroethylene board as a substrate and a modified polytetrafluoroethylene film as a coating, wherein the coating takes polytetrafluoroethylene as a raw material and takes a silica material as a doping material.
The coating of the modified polytetrafluoroethylene is prepared by calendering nano polytetrafluoroethylene to form expanded polytetrafluoroethylene and modifying the expanded polytetrafluoroethylene by trichloromethylsilane steam doping, and the preparation method of the coating comprises the following steps: a1, adding nano polytetrafluoroethylene into ethanol, stirring to form a uniform solution, standing and evaporating to form slurry, wherein the concentration of the nano polytetrafluoroethylene in the ethanol is 200g/L, the stirring speed is 2000r/min, and the standing and evaporating temperature is 90 ℃; a2, placing the slurry on a calender, standing at a constant temperature for 2 hours, and calendering to form a base film, wherein the temperature of the constant-temperature standing is 80-90 ℃, the temperature of the calendering is 100 ℃, and the thickness of the calendered base film is 500 mu m; a3, stretching, sintering and curing the base membrane to obtain the expanded polytetrafluoroethylene membrane; the stretching sequentially comprises longitudinal stretching, biaxial stretching and transverse stretching, wherein the longitudinal stretching multiple is 4 times, the temperature is 260 ℃, the biaxial stretching multiple is 4 times, the temperature is 240 ℃, and the transverse stretching temperature is 180 ℃; the sintering is carried out after the transverse stretching is finished, the sintering temperature is 320 ℃, the sintering time is 60s, and the polytetrafluoroethylene-based microporous membrane with the thickness of 50 mu m and the pore diameter of 1.4 mu m is obtained after the sintering; a4, adding trichloromethylsilane into anhydrous ether, and stirring uniformly to form a dissolved solution; then placing the expanded polytetrafluoroethylene membrane in a dry reaction kettle, introducing a dissolving solution at a constant temperature, standing for 30min, and cooling to obtain a coated expanded polytetrafluoroethylene membrane; the concentration of trichloromethylsilane in anhydrous ether is 600g/L, the constant temperature is 80 ℃, the introducing speed is 50mL/min, the standing temperature is 80 ℃, and the temperature after temperature reduction is 60 ℃; a5, placing the expanded polytetrafluoroethylene membrane in the a4 in a reaction kettle, standing for 40min, heating for 50min, and then radiating for 6min to obtain the modified polytetrafluoroethylene coating, wherein the atmosphere of the reaction kettle is an atmosphere containing water vapor, the atmosphere consists of nitrogen and water vapor, and the volume ratio of the nitrogen to the water vapor is 20: 2, standing at the temperature of 60 ℃; the temperature of the temperature raising treatment is 230 ℃.
The preparation method of the high-strength polytetrafluoroethylene composite board comprises the following steps:
step 1, sequentially carrying out sanding treatment on coarse sand and fine sand on the surface of a polytetrafluoroethylene plate to form a polytetrafluoroethylene plate with a concave-convex surface;
step 2, spraying a liquid film on the surface of the polytetrafluoroethylene plate with the concave-convex surface, then attaching the modified polytetrafluoroethylene coating to the surface of the polytetrafluoroethylene plate, and standing at constant temperature for 30min to obtain a prefabricated composite plate; the spray adopts anhydrous ether, and the spray amount is 5 mL/min; the temperature of the constant-temperature standing is 60 ℃;
and 3, carrying out constant-temperature extrusion treatment on the prefabricated composite board for 4 hours, and cooling to obtain the high-strength polytetrafluoroethylene composite board, wherein the constant-temperature extrusion temperature is 300 ℃ and the pressure is 0.7 MPa.
Example 3
The high-strength polytetrafluoroethylene composite board takes a polytetrafluoroethylene board as a substrate and a modified polytetrafluoroethylene film as a coating, wherein the coating takes polytetrafluoroethylene as a raw material and takes a silica material as a doping material.
The coating of the modified polytetrafluoroethylene is prepared by calendering nano polytetrafluoroethylene to form expanded polytetrafluoroethylene and modifying the expanded polytetrafluoroethylene by trichloromethylsilane steam doping, and the preparation method of the coating comprises the following steps: a1, adding nano polytetrafluoroethylene into ethanol, stirring to form a uniform solution, standing and evaporating to form slurry, wherein the concentration of the nano polytetrafluoroethylene in the ethanol is 150g/L, the stirring speed is 1500r/min, and the standing and evaporating temperature is 85 ℃; a2, placing the slurry on a calender, standing at a constant temperature for 2 hours, and calendering to form a base film, wherein the temperature of the constant-temperature standing is 85 ℃, the temperature of the calendering is 90 ℃, and the thickness of the calendered base film is 400 mu m; a3, stretching, sintering and curing the base membrane to obtain the expanded polytetrafluoroethylene membrane; the stretching sequentially comprises longitudinal stretching, bidirectional stretching and transverse stretching, wherein the longitudinal stretching multiple is 3 times, the temperature is 255 ℃, the bidirectional stretching multiple is 3 times, the temperature is 230 ℃, and the transverse stretching temperature is 170 ℃; the sintering is carried out after the transverse stretching is finished, the sintering temperature is 310 ℃, the sintering time is 50s, and the polytetrafluoroethylene-based microporous membrane with the thickness of 40 mu m and the pore diameter of 0.8 mu m is obtained after the sintering; a4, adding trichloromethylsilane into anhydrous ether, and stirring uniformly to form a dissolved solution; then placing the expanded polytetrafluoroethylene membrane in a dry reaction kettle, introducing a dissolving solution at a constant temperature, standing for 25min, and cooling to obtain a coated expanded polytetrafluoroethylene membrane; the concentration of trichloromethylsilane in anhydrous ether is 500g/L, the constant temperature is 75 ℃, the introducing speed is 40mL/min, the standing temperature is 75 ℃, and the temperature after temperature reduction is 50 ℃; a5, placing the expanded polytetrafluoroethylene membrane in the a4 in a reaction kettle, standing for 30min, heating for 40min, and then radiating for 5min to obtain the modified polytetrafluoroethylene coating, wherein the atmosphere of the reaction kettle is an atmosphere containing water vapor, the atmosphere consists of nitrogen and water vapor, and the volume ratio of the nitrogen to the water vapor is 20: 1, standing at 55 ℃; the temperature of the temperature raising treatment is 220 ℃.
The preparation method of the high-strength polytetrafluoroethylene composite board comprises the following steps:
step 1, sequentially carrying out sanding treatment on coarse sand and fine sand on the surface of a polytetrafluoroethylene plate to form a polytetrafluoroethylene plate with a concave-convex surface;
step 2, spraying a liquid film on the surface of the polytetrafluoroethylene plate with the concave-convex surface, then attaching the modified polytetrafluoroethylene coating to the surface of the polytetrafluoroethylene plate, and standing at constant temperature for 25min to obtain a prefabricated composite plate; the spray adopts anhydrous ether, and the spray amount is 4 mL/min; the temperature of the constant-temperature standing is 55 ℃;
and 3, carrying out constant-temperature extrusion treatment on the prefabricated composite board for 3h, and cooling to obtain the high-strength polytetrafluoroethylene composite board, wherein the constant-temperature extrusion temperature is 280 ℃ and the pressure is 0.6 MPa.
The improvement in mechanical properties can be seen with the pure polytetrafluoroethylene sheets as comparative examples and examples 1-3 as test examples, as shown in the following table:
| tensile strength/MPa | Bending strength/MPa | Compressive strength/MPa | Impact toughness/MPa | |
| Example 1 | 18.63 | 21.45 | 29.61 | 25.27 |
| Example 2 | 19.25 | 20.89 | 30.19 | 26.15 |
| Example 3 | 18.74 | 21.04 | 29.73 | 25.71 |
| Comparative example | 14.18 | 19.34 | 27.31 | 22.68 |
Meanwhile, it was confirmed by examination that the friction coefficients of examples 1 to 3 were almost identical to those of comparative example.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (7)
1. A high-strength polytetrafluoroethylene composite board is characterized in that: the polytetrafluoroethylene plate is used as a substrate, and the modified polytetrafluoroethylene film is used as a coating.
2. The high strength polytetrafluoroethylene composite sheet according to claim 1, wherein: the coating takes polytetrafluoroethylene as a raw material and takes a silica material as a doping material.
3. According to the claims: 2 the high-strength polytetrafluoroethylene composite board is characterized in that: the coating takes trichloromethylsilane as a dopant.
4. The high strength polytetrafluoroethylene composite sheet according to claim 3, wherein: the modified polytetrafluoroethylene coating is formed by calendering nano polytetrafluoroethylene into expanded polytetrafluoroethylene and modified by trichloromethylsilane steam doping to obtain the silica modified polytetrafluoroethylene composite board.
5. The high strength polytetrafluoroethylene composite sheet according to claim 1, wherein: the preparation method of the high-strength polytetrafluoroethylene composite board comprises the following steps:
step 1, sequentially carrying out sanding treatment on coarse sand and fine sand on the surface of a polytetrafluoroethylene plate to form a polytetrafluoroethylene plate with a concave-convex surface;
step 2, spraying a liquid film on the surface of the polytetrafluoroethylene plate with the concave-convex surface, then attaching the modified polytetrafluoroethylene coating to the surface of the polytetrafluoroethylene plate, and standing at constant temperature for 20-30 min to obtain a prefabricated composite plate;
and 3, extruding the prefabricated composite board at constant temperature for 2-4 h, and cooling to obtain the high-strength polytetrafluoroethylene composite board.
6. The high strength polytetrafluoroethylene composite sheet according to claim 5, wherein: the spraying in the step 2 adopts anhydrous ether, and the spraying amount is 2-5 mL/min; the temperature of the constant temperature standing is 50-60 ℃.
7. The high strength polytetrafluoroethylene composite sheet according to claim 5, wherein: the temperature of the constant-temperature extrusion in the step 3 is 270-300 ℃, and the pressure is 0.4-0.7 MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115301524A (en) * | 2022-06-15 | 2022-11-08 | 江苏新合益机械有限公司 | Densification treatment method for piston rod surface |
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